Potential sweep techniques, applied

The potentiostatic technique has a number of variations and the potential may be increased or decreased incrementally, changed continuously at a predetermined rate (potential sweep) or applied as pulses of very short duration. The applications of the potentiostatic technique are considered in detail in Sections 1.4, 1.5 and 19.2, and will not be considered here. 

Historically, the potential sweep technique and cyclic voltammetry were developed for analysis (as successors to polarography) and much of the theoretical development is concerned with the situation under conditions of diffusion control, for that is where the analytical applications are most readily made. In many of these approaches, the underlying assumption is that the electron transfer that must necessarily occur at the interface is a fast process and plays little part in determining the dependence of the observed current upon potential or upon the concentration of the reactant. However, these assumptions may not always apply. 

In potential-sweep techniques, the current flowing at the WE/solution interface is monitored as a function of the potential applied to it. We consider three such volta-mmetric techniques linear sweep voltammetry (LSV), cyclic voltammetry (CV), and hydrodynamic voltammetry (Fig. 20.4). The voltammogram obtained in each case may be regarded as the electrochemical equivalent of a spectrum obtained in a spectrophotometric technique. Indeed, the term electrochemical spectroscopy has been applied to CV [56], and it is worth noting that the independent variable in both cases is related to energy—wavelength in the case of spectroscopy and potential in the case of CV. The potential is swept linearly at I V/s so that the potential at any time is (/) = E vt. 

Many investigators have used different techniques to study the electrochemical behavior of different sulphide mineral electrodes in solutions of different compositions. Linear potential sweep voltammetry (LPSV), and cyclic voltammetry (CV) have been perhaps, used most extensively and applied successfully to the investigation of reactions of sulphide minerals with aqueous systems. These techniques have provided valuable information on the extent of oxidation as a function of potential for various solution conditions and have allowed the identity of the surface products to be deduced. 

Linear sweep voltammetry Ep measurements have not been applied extensively for the study of heterogeneous charge transfer kinetics. A serious problem with the use of this method is that Ep in itself is not significant in this respect but rather Ep — Etev is the quantity of interest. While AEP in CV is readily measured, this cannot be said for Etev using only LSV as a measurement technique. Therefore, there does not appear to be any advantage in LSV for the study of electrode kinetics. A more detailed analysis of the LSV wave, by convolution potential sweep or normalized potential sweep voltammetry (both to be discussed later) can provide both a and k°. 

A complete comprehension of Single Pulse electrochemical techniques is fundamental for the study of more complex techniques that will be analyzed in the following chapters. Hence, the concept of half-wave potential, for example, will be defined here and then characterized in all electrochemical techniques [1, 3, 8]. Moreover, when very small electrodes are used, a stationary current-potential response is reached. This is independent of the conditions of the system prior to each potential step and even of the way the current-potential was obtained (i.e., by means of a controlled potential technique or a controlled current one) [9, 10]. So, the stationary solutions deduced in this chapter for the current-potential curves for single potential step techniques are applicable to any multipotential step or sweep technique such as Staircase Voltammetry or Cyclic Voltammetry. Moreover, many of the functional dependences shown in this chapter for different diffusion fields are maintained in the following chapters when multipulse techniques are described if the superposition principle can be applied. 

In this section, we will show that the stationary responses obtained at microelectrodes are independent of whether the electrochemical technique employed was under controlled potential conditions or under controlled current conditions, and therefore, they show a universal behavior. In other words, the time independence of the I/E curves yields unique responses independently of whether they were obtained from a voltammetric experiment (by applying any variable on time potential), or from chronopotentiometry (by applying any variable on time current). Hence, the equations presented in this section are applicable to any multipotential step or sweep technique such as Staircase Voltammetry or Cyclic Voltammetry. 

Linear sweep voltammetry (LSV), also known as linear sweep chronoamperometry, is a potential sweep method where the applied potential (E) is ramped in a linear fashion while measming cnrrent (i). LSV is the simplest technique that uses this waveform. The potential range that is scanned begins at an initial or start potential and ends at a final potential. It is best to start the scan at rest potential, the potential of zero current. For a reversible couple, the peak potential can be calcnlated nsing equation (6). ... 

The technique of cyclic voltammetry or, more precisely, linear potential sweep chronoamperometry, is used routinely in aqueous electrochemistry to study the mechanisms of electrochemical reactions. Currently, cyclic voltammetry has become a very popular technique for initial electrochemical studies of new systems and has proven very useful in obtaining information about fairly complicated electrochemical reactions. There have been some reported applications of cyclic voltammetry for solid electrochemical systems. It is worth pointing out that, although the theory of cyclic voltammetry originally developed by Sevick, ° Randles, Delahay, ° and Srinivasan and Gileadi" and lucidly presented by Bard and Faulkner, is very well established and understood in aqueous electrochemistry, one must be cautious when applying this theory to solid electrolyte systems of the type described here, as some non-trivial refinements may be necessary. 

Basically, experimental approaches to ion transfer kinetics rely on classical galvanostatic [152] or potentiostatic [146] techniques, such as chronopotentiometry [118, 138], chronocoulometry [124], cyclic voltammetry [146], convolution potential sweep voltammetry [147], phase selective ac voltammetry [142], or equilibrium impedance measurements [148]. These techniques were applied mostly to liquid-liquid interfaces with a macroscopic area (typically around 0.1 cm ). However, microelectrode methodology has been successfully introduced into liquid-liquid electrochemistry as a novel electroanalytical tool by Senda and coworkers [153] and... 

Figure 1.11 Synchronisation between the collection of FTIR spectra and the potential applied to the working electrode during potential modulation techniques. It is assumed that single-sided interferograms are collected during the forward sweep of the moving mirror (ZPD = zero path difference for the two paths of the interferometer).

The technique of controlled-potential cathodic deposition followed by anodic stripping with a linear potential sweep has been applied to the determinations of a number of metals (e.g., Bi, Cd, Cu, In, Pb, and Zn) either alone or in mixtures (Figure 11.8.5). An increase in sensitivity can be obtained by using pulse polarographic, square wave, or coulostatic stripping techniques. Other variants, such as stripping by a potential step, current step, or more elaborate programs (e.g., an anodic potential step for a short time followed by a cathodic sweep) have also been proposed (68-74). 

The measurement of the current for a redox process as a function of an applied potential yields a voltammogram characteristic of the analyte of interest. The particular features, such as peak potentials, halfwave potentials, relative peak/wave height of a voltammogram give qualitative information about the analyte electrochemistry within the sample being studied, whilst quantitative data can also be determined. There is a wealth of voltammetric techniques, which are linked to the form of potential program and mode of current measurement adopted. Potential-step and potential-sweep... 

Differential pulse voltammetry (DPV) is essentially an instrumental manipulation of chronoamperometry. It provides very high sensitivity because charging current is almost wholly eliminated. More important for CNS applications, it often helps to resolve oxidations which overlap in potential. The method combines linear potential sweep and square-wave techniques. The applied signal is shown in Fig. 16A and consists of short-duration square-wave pulses (<100 msec) with constant amplitude (typically 20 or 50 mV) and fixed repetition interval, superimposed on a slow linear potential scan. The Fapp waveform can be generated with a laboratory-built potentiostat, but most DPV work is done with a commercial pulse polarograph (see Appendix). The inset of Fig. 16A shows an enlargement of one pulse. The current is measured just before the pulse... 

---